Zeolite-containing catalyst and method for producing the same, and method for producing propylene

ABSTRACT

The present invention provides a zeolite-containing catalyst having excellent shape, fluidity and mechanical strength as a catalyst for a fluidized bed reaction. The present invention provides a zeolite-containing catalyst which is a particulate catalyst containing zeolite and silica, wherein the catalyst has an average particle diameter of 20 to 300 μm and the ratio of the void area in the cross-section of the particle is 30% or less relative to the cross-section area of the particle.

TECHNICAL FIELD

The present invention relates to a zeolite-containing catalystcontaining zeolite and silica and its production method, and to aproduction method of propylene using the zeolite-containing catalyst.

BACKGROUND ART

In a fluidized bed reaction, in general, a reactive gas is supplied froma lower part of a reactor filled with a catalyst and catalyst particlesare fluidized by the gas flow in the reactor, and then the catalystparticles are contacted with the reactive gas to allow the reaction toproceed. Here, the catalyst used for the fluidized bed reaction isrequired to have physical properties suitable for the fluidized bedreaction such as chemical performance, particle shape, size,distribution, fluidity and strength.

There is described a suitable property of catalyst particles forachieving a preferable fluidized state in the fluidized bed reactionstep, for example, in page 16 of “Fluidized Bed Handbook” (edited by theAssociation of Powder Process Industry & Engineering, Japan, andpublished by Baifukan on Mar. 25, 1999). The document describes: “Asufficiently fast mass transfer between gas bubbles and an emulsionphase containing a catalyst is preferable in improving the reaction rateand selection rate. For this purpose, smaller gas bubbles are preferableand it is considered to be preferable that the particles are small andhave a smooth and slippery surface. And, it is generally said thatpreferred particles have a bulk density of 0.6 to 1.0 g·cm⁻³ and anaverage diameter of 60 to 80 μm.” In addition, if there occurs attritionor fracture of catalyst particles due to collision or contact betweencatalyst particles, between catalyst particles and the reactor, andbetween the catalyst particles and the reactive gas, accompanied by thefluidization of the catalyst, the fluidity of catalyst particles isdecreased and fractured particles are scattered. Consequently, as theproperty of the fluidized bed reaction catalyst, mechanical strengthsufficiently enough to withstand attrition or fracture is also demanded.

That is, a catalyst used for a fluidized bed reaction is required tohave a shape, a particle size distribution and the like excellent influidity, and mechanical strength (attrition resistance) to withstandcollision or contact between catalyst particles, between catalystparticles and the reactor, and between the catalyst particles and thereactive gas.

In order that the catalyst has mechanical strength suitable for thefluidized bed reaction, there is known a method in which a catalystactive component such as zeolite is molded with a support componentwhich becomes a binder such as alumina, silica and clay, and the moldedproduct is calcined. For example, in Patent Document 1, there isdescribed a method in which a buffered silica sol is prepared by addingsulfuric acid and aluminum sulfate to sodium silicate, and to thebuffered silica sol are added clay and zeolite to prepare a raw materialslurry which is adjusted to a specific pH, followed by spray drying theslurry to produce a hydrocarbon conversion catalyst having highattrition resistance. In addition, in Patent Document 2, there isdisclosed a production method of a fluidized catalytic cracking catalystin which the catalyst is a fluidized bed catalyst with meso-porositycomprising zeolite, gibbsite (aluminum hydroxide), a rare earth metaland a silica matrix, and the silica matrix is prepared from a silica solprepared by an ion exchange method or from an acidic silica solcontaining sodium silicate, sulfuric acid and aluminum sulfate.

-   [Patent Document 1] Japanese Patent Application Laid-Open No.    51-40390-   [Patent Document 2] Japanese Patent Application Laid-Open No.    10-146529

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

According to the findings of the present inventors, the mechanicalstrength of a zeolite-based catalyst has a correlation with the surfaceshape, and a zeolite-based catalyst having a smoother surface shapetends to have higher mechanical strength. In addition, a zeolite-basedcatalyst having a particle shape nearer to a sphere is preferable fromthe viewpoint of mechanical strength, and a catalyst having nosufficient mechanical strength has a higher tendency of having a shapein which gases and the like incorporated are blown out from a part ofthe sphere.

On the other hand, the present inventors conducted a follow-up study onthe catalyst preparation methods described in Japanese Patent Laid-OpenNo. 51-40390 and Japanese Patent Laid-Open No. 10-146529. The resultsshowed that significant unevenness was observed on the surfaces of boththe catalysts obtained by the methods described in these documents andboth the catalysts had a shape far from a smooth sphere.

In light of the above circumstances, an object of the present inventionis to provide a zeolite-containing catalyst having excellent shape,fluidity and mechanical strength as a catalyst for a fluidized bedreaction and a method for producing the catalyst, and a method for theproduction of propylene using the zeolite-containing catalyst.

Means for Solving the Problems

As a result of earnest studies to solve the above-described problems,the present inventors have found that there may be produced azeolite-containing catalyst having excellent mechanical strength bydecreasing the void content inside the catalyst, and have completed thepresent invention.

That is, the present invention is as follows:

[1] A zeolite-containing catalyst which is a particulate catalystcontaining zeolite and silica, wherein the catalyst has an averageparticle diameter of 20 to 300 μm and the ratio of the void area in thecross-section of said particle is 30% or less relative to thecross-section area of the particle.

[2] The zeolite-containing catalyst according to [1], wherein saidzeolite is an MFI-type zeolite.

[3] The zeolite-containing catalyst according to [1] or [2], wherein thecontent rate of said zeolite is from 10 to 90% by mass, the content rateof said silica is from 10 to 90% by mass, and the total content rate ofsaid zeolite and said silica is 50% by mass or more.

[4] A method for producing a zeolite-containing catalyst according toany one of [1] to [3], comprising: the steps of obtaining a dried powderby spray drying a raw material mixture containing zeolite and colloidalsilica; and calcining said dried powder, wherein said raw materialmixture contains at least one water-soluble compound selected from thegroup consisting of a nitrate salt, an acetate salt, a carbonate salt, asulfate salt and a chloride in a mass ratio of 0.01 to 5.0 relative tothe silica contained in said colloidal silica.

[5] The method for producing a zeolite-containing catalyst according to[4], wherein the ratio of the mass of said colloidal silica to the totalamount of silica contained in said raw material mixture is 50% by massor more.

[6] The method for producing a zeolite-containing catalyst according to[4] or [5], wherein said raw material mixture is acidic.

[7] The method for producing a zeolite-containing catalyst according toany one of [4] to [6], wherein said water-soluble compound is at leastone selected from the group consisting of ammonium nitrate, ammoniumacetate, ammonium carbonate, ammonium sulfate and ammonium chloride.

[8] A method for producing propylene comprising the step of contacting azeolite-containing catalyst according to any one of [1] to [3] with ahydrocarbon and/or an alcohol in a fluidized bed reactor.

EFFECT OF THE INVENTION

The present invention can provide a zeolite-containing catalyst havingexcellent shape, fluidity and mechanical strength as a catalyst for afluidized bed reaction and a method for producing the catalyst, and amethod for the production of propylene using the zeolite-containingcatalyst.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an electron microscope photograph (at a magnification of 150times) showing a zeolite-containing catalyst of Example 1;

FIG. 2 is an electron microscope photograph (at a magnification of 1500times) showing a particle cross-section of the zeolite-containingcatalyst of Example 1;

FIG. 3 is an electron microscope photograph (at a magnification of 150times) showing a zeolite-containing catalyst of Example 2;

FIG. 4 is an electron microscope photograph (at a magnification of 1700times) showing a particle cross-section of the zeolite-containingcatalyst of Example 2;

FIG. 5 is an electron microscope photograph (at a magnification of 150times) showing a zeolite-containing catalyst of Example 3;

FIG. 6 is an electron microscope photograph (at a magnification of 1600times) showing a particle cross-section of the zeolite-containingcatalyst of Example 3;

FIG. 7 is an electron microscope photograph (at a magnification of 1700times) showing a particle surface of the zeolite-containing catalyst ofExample 2;

FIG. 8 is an electron microscope photograph (at a magnification of 1600times) showing a particle surface of the zeolite-containing catalyst ofExample 25;

FIG. 9 is an electron microscope photograph (at a magnification of 150times) showing a zeolite-containing catalyst of Example 26 afteroperation for 1000 hours;

FIG. 10 is an electron microscope photograph (at a magnification of 150times) showing a zeolite-containing catalyst of Comparative Example 1;

FIG. 11 is an electron microscope photograph (at a magnification of 1600times) showing a particle cross-section of the zeolite-containingcatalyst of Comparative Example 1;

FIG. 12 is an electron microscope photograph (at a magnification of 150times) showing a zeolite-containing catalyst of Comparative Example 2;

FIG. 13 is an electron microscope photograph (at a magnification of 1500times) showing a particle cross-section of the zeolite-containingcatalyst of Comparative Example 2;

FIG. 14 is an electron microscope photograph (at a magnification of 150times) showing a zeolite-containing catalyst of Comparative Example 3;

FIG. 15 is an electron microscope photograph (at a magnification of 1500times) showing a particle cross-section of the zeolite-containingcatalyst of Comparative Example 3;

FIG. 16 is an electron microscope photograph (at a magnification of 150times) showing a zeolite-containing catalyst of Comparative Example 8;

FIG. 17 is an electron microscope photograph (at a magnification of 1500times) showing a particle cross-section of the zeolite-containingcatalyst of Comparative Example 8;

FIG. 18 shows the change over time of the ethylene conversion rate whenperforming a reaction for producing propylene from a raw materialcontaining ethylene in Examples 27 to 30; and

FIG. 19 shows the change over time of the ethylene conversion rate whenperforming a reaction for producing propylene from a raw materialcontaining ethylene in Example 31 and Comparative Example 9.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, there will be described embodiments (hereinafter, referredto as “the present embodiment”) for carrying out the present inventionin detail. In addition, the present invention is not limited to thefollowing embodiments, and various modifications may be made within thegist of the present invention.

Further, the term “silica” as used herein refers to silica which iscontained in a silica raw material used for the production of azeolite-containing catalyst, and unless otherwise specified, it does notmean the silica constituting zeolite.

[Zeolite-Containing Catalyst]

The zeolite-containing catalyst of the present invention is aparticulate catalyst containing zeolite and silica, in which theparticle has an average particle diameter of 20 to 300 μm and the ratioof the void area in the cross-section of the particle is 30% or lessrelative to the cross-section area of the particle.

The term “zeolite” as used herein refers to a crystalline porousaluminosilicate or a metallosilicate (zeolite in which a part or all ofthe aluminum atoms constituting the skeleton of a crystalline porousaluminosilicate is substituted with a substitutable element such as Ga,Fe, B, Cr and Ti), and includes a phosphate-based porous crystal havinga structure similar to or same as that of the aluminosilicate andmetallosilicate.

Specifically, a zeolite having a small pore diameter (structure ofoxygen 8-membered ring or less) includes chabazite (CHA: a frameworktype code name specified by International Zeolite Association, the sameshall apply hereinafter), erionite (ER1) and A type (LHA). A zeolitehaving intermediate diameter (structure of oxygen 10-membered ring)includes ferierite (FER), ZMS-11 (MEL), ZSM-5 (MFI) and AlPO₄-11 (AEL).In addition, a zeolite having a large pore diameter (structure of oxygen12-membered ring) includes X type (FAU), Y type (FAU), faujasite (FAU),β type (BEA), mordenite (MOR), ZSM-12 (MTW) and ALPO₄-5 (AFI). Further,a zeolite having an ultralarge pore diameter (structure of oxygen14-membered ring or more) includes UTD-1 (DON), CIT-5 (CFI) and VPI-5(VFI).

Among these, preferred is a zeolite having an intermediate pore diametercomposed of oxygen 10-membered ring, more preferred is an MFI-typezeolite and especially preferred is ZSM-5. When a catalyst containing azeolite having such an intermediate pore diameter is used for aconversion reaction of hydrocarbon which is conducted in a gas phasesuch as a fluid catalytic cracking (FCC) reaction, the coke contentgenerated with the reaction tends to be small compared to the case wherea zeolite having a large pore diameter is used. Accordingly, since poreocclusion due to the coke is unlikely to occur and the catalyst lifetimemay be extended, preferred is the zeolite having an intermediate porediameter. In addition, the zeolite having an intermediate pore diameteris preferable because the reacting molecules of an alcohol or ahydrocarbon or the like easily penetrate into pores and the active siteson the catalyst may be effectively used, compared to the zeolite havinga small pore diameter. Further, the zeolite having a small pore diameterhas a greater tendency of decreasing the activity by the coke generatedwith the reaction than the zeolite having an intermediate pore diameter.

Among the zeolites having an intermediate pore diameter, especiallypreferred is a zeolite (MFI-type zeolite; especially ZSM-5) having anMFI-type structure because it has a high heat resistance and acharacteristic catalytic activity due to the shape selectivity andstrong solid acidity.

The cation-type zeolite may be H⁺ type and may be one in which a part orall of H⁺ is substituted with a metal cation.

Especially, when the zeolite-containing catalyst of the presentembodiment is used as a fluidized bed reaction catalyst in producingpropylene by contacting with a hydrocarbon containing ethylene, thezeolite-containing catalyst preferably contains at least one metalselected from the group consisting of metals belonging to Group IB inthe Periodic Table, that is, copper, silver and gold. The metalincorporated in the zeolite-containing catalyst is preferably copperand/or silver, and is especially preferably silver. In addition, in thepresent specification, the “Periodic Table” refers to the periodic tabledescribed in Page 1 to 15, CRC Handbook of Chemistry and Physics, 75thedition, edited by David R. Lide, et al., published by CRC Press Inc.(1994 to 1995).

The metal incorporated in the zeolite-containing catalyst is containedin the zeolite in the catalyst in the corresponding cation state or issupported on a catalyst.

In addition, a zeolite modified with a phosphor compound is alsopreferably used. The phosphorus compound includes phosphoric acid,phosphorous acid, hypophosphorous acid, pyrophosphoric acid,polyphosphoric acid, ammonium monohydrogen phosphate, ammoniumdihydrogen phosphate, ammonium phosphate and aluminum phosphate. Theremay be used a catalyst obtained by absorbing or impregnating thesecompounds in an amount of 0.1 to 5% by mass in the zeolite as aphosphorus element.

The zeolite-containing catalyst of the present embodiment has an averageparticle diameter in the range of 20 to 300 μm. The average particlediameter is preferably from 20 to 200 μm, more preferably from 40 to 100μm, further more preferably from 40 to 80 μm and especially preferablyfrom 40 to 60 μm.

In addition, from the viewpoint of fluidity, the zeolite-containingcatalyst of the present embodiment preferably has a particle sizedistribution such that the particle diameters of 80% or more particlesin the whole particles are in the range from 2 to 0.2 times the averageparticle diameter.

The terms “particle diameter” and “particle size distribution” as usedherein mean a value measured by a laser diffraction/scattering typeparticle size analyzer. In addition, the term “average particlediameter” as used herein means a cumulative average diameter which is avalue obtained by measuring the particle size distribution (ratio ofparticles present in a fixed particle size range) of a powderyzeolite-containing catalyst by the above analyzer and determining thecumulative particle size distribution by defining the whole volume as100%. The point where the cumulative is 50% is a particle diameter, thatis, a cumulative average diameter (a center diameter, a mediandiameter).

From the viewpoint of fluidity and strength, the zeolite-containingcatalyst of the present embodiment preferably is spherical. As shown inFIGS. 10 to 17 described later in detail, the conventionalzeolite-containing catalyst is far from a spherical shape because itfrequently has a shape in which a hole formed in the vicinity of thecenter is ruptured or the particle surface has significant unevenness.The term “spherical shape” as used herein as a catalyst shape is notalways required to be a true sphere or a nearly true sphere because thepurpose is to compare it with such a conventional catalyst shape, andmeans to a degree that the catalyst of the present embodiment is not ina ruptured shape and has no significant protrusions or dents. However,needless to say, it is more preferable that the shape of thezeolite-containing catalyst is apparently near a true sphere. Aspherical zeolite-containing catalyst is also advantageous in durabilitybecause it is smoothly fluidized in a fluidized bed reactor and tends toexhibit large strength.

If the zeolite-containing catalyst has an average particle diameter ofless than 20 μm, the angle of repose, which is a measure of fluidity ofa catalyst, tends to increase, and when used as a fluidized bed reactioncatalyst, the fluidity of the catalyst is deteriorated. If thezeolite-containing catalyst has an average particle diameter exceeding300 μm, the mechanical strength of the catalyst tends to decrease, andwhen used as a fluidized bed reaction catalyst, the central portion ofthe catalyst particles tends not to be effectively used for thereaction.

The zeolite-containing catalyst of the present embodiment has astructure in which the ratio of the void area in the cross-section ofthe particle is 30% or less relative to the cross-section area of theparticle. The ratio of the void area is preferably 20% or less, morepreferably 15% or less and especially preferably 10% or less.

The term “the ratio of the void area in the cross-section of theparticle” as used herein means a value measured as follows.

That is, firstly, the particles of the zeolite-containing catalyst areembedded with a resin, followed by grinding it to scrape away thecross-section of the catalyst particles. The cross-section is observedby an electron microscope equipped with an image analysis device and thecross-section area of one particle and the area of the void portion inthe cross-section of the particle are measured at a magnification of 800to 2000 times. Here, in case of a catalyst having a hole as in the aboveconventional example, “the cross-section area” is defined as a valueincluding the area of the void portion. In addition, in case of theparticle having a shape in which a hole is ruptured, both ends ofportions (opening portion) in which a part of the circumference is cutby “rapture” are connected with a straight line so as to occlude theopening portion, and the area in the range surrounded by the straightline and the outer circumference is defined as the cross-section area.For example, in case of the catalyst shown in FIG. 11, the substantialportion is a C-character type, but the area of the whole rangesurrounded by the straight line connecting the opening portion and thesubstantial portion of the C-character type is defined as thecross-section area (the cross-section area includes the area of theopening portion observed black in the vicinity of the center in thefigure). The area of the void portion in this example is defined as thearea in the portion surrounded by the straight line connecting theopening portion and the inner wall of the substantial portion of theC-character type.

Subsequently, the ratio of the area of the void portion to thecross-section area of particles is calculated. Then, a series ofoperations are carried out for 100 particles and the arithmetic average(arithmetical mean) value is defined as the ratio of the void area inthe cross section of the particle. However, in order to measure thecross section in the vicinity of the center of the particle, particleshaving a diameter in the range of ±10% of the average particle diameterare selected as 100 particles to be measured.

If the ratio of the void area exceeds 30%, the mechanical strength ofthe particle tends to decrease.

As described above, the conventional zeolite-containing catalyst had ashape in which a large hole is formed in the vicinity of the center, ora hole is ruptured, or the particle surface has significant unevenness.Until now, there has never been found out a zeolite-containing catalyst,which has a sophisticated structure in which the void portion inside theparticle is extremely small and thus is extremely high in mechanicalstrength, as with the zeolite-containing catalyst of the presentinvention. If a catalyst used for a fluidized bed reaction has highmechanical strength, it is extremely important for an industrial processbecause powderization of the catalyst is unlikely to occur even duringthe long period of use and a suitable fluidized state may be stablymaintained.

As described above, since a zeolite-containing catalyst having highmechanical strength exhibits a tendency that it is not easily abraded,the mechanical strength of the catalyst depends on the attrition loss ofthe catalyst. The attrition loss for a fixed period time is measured byusing a jet fluidic apparatus. The attrition loss is preferably 3% bymass or less, more preferably 2% by mass or less and especiallypreferably 1% by mass or less.

The zeolite-containing catalyst of the present embodiment has an angleof repose of preferably 25 to 30° and more preferably from 25 to 28°. Ifthe angle of repose is 30° or less, the fluidity of the catalyst is morepreferable. The angle of repose is measured by the method described inExample described later.

Regarding the composition of the zeolite-containing catalyst of thepresent embodiment, in a shape after calcining, preferably, (I) thecontent rate of the zeolite is from 10 to 90% by mass, (II) the contentrate of the silica is from 10 to 90% by mass, and (III) the totalcontent rate of the zeolite and silica is 50% by mass or more withrespect to the total content of the zeolite-containing catalyst. Morepreferably, (I) the content rate of the zeolite is from 20 to 60% bymass, (II) the content rate of the silica is from 80 to 40% by mass, and(III) the total content rate of the zeolite and silica is 70% by mass ormore. Much more preferably, (I) the content rate of the zeolite is from30 to 50% by mass, (II) the content rate of the silica is from 70 to 50%by mass, and (III) the total content rate of the zeolite and silica is90% by mass or more.

(I) If the content rate of the zeolite is less than 10% by mass, theactivity per unit amount of catalyst becomes low and the required amountof the catalyst tends to increase in order to obtain a desired activitybecause the content of the zeolite which is an active component issmall. If the content rate of the zeolite exceeds 90% by mass, themechanical strength of catalyst particles tends to decrease because thezeolite itself does not have preferable adhesiveness.

(II) If the content rate of the silica is less than 10% by mass, themechanical strength of catalyst particles tends to decrease for the samereason as above. If the content rate of the silica exceeds 90% by mass,the activity per unit amount of catalyst becomes low and the requiredamount of the catalyst tends to increase in order to obtain a desiredactivity for the same reason as above.

(III) If the total content rate of the zeolite and silica is less than50% by mass, the activity per unit amount of catalyst becomes low andthe required amount of the catalyst tends to increase in order to obtaina desired activity for the same reason as above, and the mechanicalstrength of catalyst particles tends to decrease.

Since the zeolite-containing catalyst of the present embodiment has aspecific average particle diameter and the ratio of the void area in thecross-section of the particle is 30% or less relative to thecross-section area of the particle, it has high fluidity and mechanicalstrength. For this reason, it is especially preferable as a catalyst fora fluidized bed reaction.

[Method for Production of Zeolite-Containing Catalyst]

The method for the production of the zeolite-containing catalyst of thepresent embodiment is a method for obtaining a zeolite-containingcatalyst which has an average particle diameter of 20 to 300 μm and inwhich the ratio of the void area in the cross-section of the particle is30% or less relative to the cross-section area of the particle. In orderto obtain such a zeolite-containing catalyst, various conditions asdescribed below in detail need only to be adjusted. The method for theproduction of the zeolite-containing catalyst of the present embodimentpreferably comprises: (ii) a step of obtaining dried powders by spraydrying a raw material mixture containing zeolite and a colloidal silica;and (iii) a step of calcining the dried powders. The method for theproduction of the zeolite-containing catalyst may comprise: prior to theabove step (ii), (i) a step of preparing the raw material mixturecontaining zeolite and a colloidal silica; and/or after the step (iii),(iv) a step of ion-exchanging calcined powders obtained by calcining.

[Step (i): Preparation Step of Raw Material Mixture]

The step (i) is a step of preparing a raw material mixture (hereinafter,also referred to as a “raw material slurry”) containing zeolite, acolloidal silica and at least one water-soluble compound selected fromthe group consisting of a nitrate salt, an acetate salt, a carbonatesalt, a sulfate salt and a chloride.

The molar ratio SiO₂/Al₂O₃ (silica/alumina ratio) of the zeolite ispreferably from 15 to 1000 and more preferably from 20 to 300. Inaddition, when zeolite is a metallosilicate, the molar ratio SiO₂/Al₂O₃(silica/alumina ratio) is calculated by assuming the number of moles ofalumina containing an aluminum atom substituted with a substitutableelement such as Ga, Fe, B, Cr and Ti as the number of moles of aluminapresent in the metallosilicate.

The raw material zeolite is preferably in a state in which primaryparticles of the zeolite are dispersed. In general, zeolite frequentlyforms a secondary agglomeration because primary particles of the zeolitehaving a diameter of approximately 0.05 to 10 μm are partly bondedtogether. When the zeolite which remains to form a secondaryagglomeration is molded with a binder such as silica, the surface of themolded particles becomes rough and mechanical strength tends to decreasebecause a void portion is likely to be formed inside the particle. Forthis reason, if the zeolite forms a secondary agglomeration, it ispreferable that the zeolite is used by mechanically pulverizing using ajet mill or the like to deagglomerate. As the pulverizing method ofzeolite, it is more preferable to use a method of using a jet mill inwhich the pulverizing treatment is performed by jetting compressed airat ultrahigh speed than to use a conventional ball mill. On thisoccasion, it is especially preferable that zeolite is deagglomerateduntil the average particle diameter of the zeolite becomes in the rangeof 0.05 to 5 μm.

In addition, the agglomeration state of the zeolite can be observed byan electron microscope. Further, the average particle diameter of thezeolite is measured by a laser diffraction/scattering type particle sizeanalyzer in the same manner as above.

The colloidal silica used for a catalyst raw material is preferablyprepared by an ion-exchange method.

In general, water glass (sodium silicate) is frequently used as a rawmaterial for the production of a fluidized bed catalyst. However, theresults of studies of the present inventors showed that when water glassis used as a main component of a binder silica, not only the shape of aparticle surface of a catalyst tends to be deteriorated but also thereis a problem with respect to catalyst performance. That is, if sodiumsilicate is used as a raw material of the binder silica, sodium, whichis a catalyst poison for a solid acid catalyst, is contained in a largeamount in a catalyst. Although it is possible to reduce theconcentration of sodium contained in a binder, in order to remove sodiumfrom the catalyst to a low concentration where the catalyst reaction isnot adversely affected, there are required extremely complicatedoperations such as plural times of hot water washing and ion-exchangingusing a special device for preventing the breakage of particles.

On the other hand, when a colloidal silica prepared by an ion-exchangemethod is used as a main component, the surface of a catalyst particlebecomes smooth. As used herein, “the surface (of a particle) is smooth”refers to that the surface of the particle apparently has no unevennesswhen observation is carried out by a microscope photograph at amagnification of 150 times. In addition, when the colloidal silica isused as a main component, since the sodium content contained in the rawmaterial is small, the ion-exchanging step is not always required andsodium may be removed by a convenient operation.

However, when the colloidal silica is simply used instead of water glassin the conventional technique, there is a problem that a large hole isformed at the center of a catalyst molded by spray drying and thecatalyst particles become brittle. On the other hand, in the presentembodiment, the problem has been solved by allowing a predeterminedamount of the water-soluble compound described later to coexist with acatalyst raw material.

The larger the ratio of the silica (derived from the colloidal silica)obtained by using the colloidal silica as a raw material to the totalamount of the silica (excluding the silica constituting zeolite)contained in the zeolite-containing catalyst, the more preferable.Specifically, the ratio is preferably 50% by mass or more, morepreferably 60% by mass or more, further more preferably 70% by mass ormore, still further more preferably 80% by mass or more and especiallypreferably 90% by mass or more.

Similarly, the ratio of the colloidal silica to the total amount of thesilica (excluding the silica constituting zeolite) contained in the rawmaterial mixture is preferably 50% by mass or more, more preferably 60%by mass or more, further more preferably 70% by mass or more, especiallypreferably 80% by mass or more and extremely preferably 90% by mass ormore. In addition, for example, when the silica source contained in theraw material mixture is water glass and the colloidal silica, the ratioof the colloidal silica to the total amount of the silica contained inthe raw material mixture means the ratio (the silica contained by thecolloidal silica)/(the silica contained by the colloidal silica+thesilica contained by the water glass) on a mass basis. As the ratio ofthe colloidal silica contained in the raw material mixture is higher,the surface of the resulting catalyst tends to become smoother.Especially if the ratio is 70% by mass or higher, there are lessparticles having protrusions or depressions on the surface (40% orless), even when observation is carried out at a magnification of 1600times or more. In addition, “protrusions or depressions” show a statewhere local unevenness is generated on the surface and are differentfrom a state where linear cracks are formed on the surface.

As the colloidal silica prepared by an ion-exchange method, acommercially available one may be used. A colloidal silica stabilized byammonia or amine is especially preferable in that the content of analkali metal is small. The smaller the content (by mass) of an alkalimetal in the colloidal silica, the more preferable, and the content ispreferably 1000 ppm or less and more preferably 250 ppm or less as analkali metal. The alkali metal contained in the zeolite-containingcatalyst may be reduced by using a colloidal silica having a smallcontent of an alkali metal as a main component of silica. The content ofan alkali metal with respect to the total mass of the zeolite-containingcatalyst is preferably 5000 ppm or less, more preferably from 10 to 3000ppm, further more preferably from 10 to 1000 ppm, still further morepreferably from 10 to 300 ppm and especially preferably from 10 to 100ppm. If the content of an alkali metal exceeds 5000 ppm, the catalyticactivity tends to decrease. On the other hand, if the content of analkali metal is less than 10 ppm, there is no useful effect on catalyticactivity. If a plurality of alkali metals is contained in thezeolite-containing catalyst, the total content of each alkali metal ispreferably in the above range.

In order to measure the content of the alkali metal contained in thezeolite-containing catalyst, firstly, the catalyst is dissolved in royalwater at 210° C. using a microwave (produced by Milestone Inc., Type:ETOS PLUS) and a small amount of residue is filtered. Thereafter, theamount of the alkali metal in the filtrate is measured by a conventionalmethod using an ICP emission spectroscopy. The content of the alkalimetal in the zeolite-containing catalyst may be derived from the contentof the alkali metal contained in the filtrate. The measurementconditions of the ICP emission analysis may be set at a high frequencypower of 1 kw, a plasma gas flow rate of 13 L/min, a sheath gas flowrate of 0.15 L/min and a nebulizer gas flow rate of 0.25 L/min.

The silica contained in the colloidal silica has an average particlediameter of preferably from 3 to 50 nm and more preferably from 4 to 25nm. If the silica in the colloidal silica has an average particlediameter of 50 nm or less, the mechanical strength of molded particlestends to further increase. The average particle diameter of silica ismeasured by a laser-type dynamic light-scattering particle sizedistribution analyzer.

To the raw material slurry is added at least one water-soluble compoundselected from the group consisting of a nitrate salt, an acetate salt, acarbonate salt, a sulfate salt and a chloride.

As described in Page 1014 of Miniature Version of ComprehensiveDictionary of Chemistry, 39th printing (published by Kyoritsu ShuppanCo., Ltd., on Jun. 15, 2006), the term “salt” as used herein refers to acompound generated by the neutralization reaction of an acid and a base,which is composed of the negative component of the acid and the positivecomponent of the base.

In addition, the term “water-soluble compound” as used here means acompound having a solubility of 1 g or more in 100 g of water at 25° C.The water-soluble compound preferably is a compound having a solubilityof 10 g or more in 100 g of water at 25° C., and for example, includesan ammonium salt, an aluminum salt and a sodium salt.

A more preferred water-soluble compound is an ammonium salt which ishigh in water-solubility and may be decomposed and removed from acatalyst in the calcining step described later. More specifically, it ismore preferable that the water-soluble compound is one or more ammoniumsalts selected from the group consisting of ammonium nitrate, ammoniumacetate, ammonium carbonate, ammonium sulfate and ammonium chloride, andmost preferred is ammonium nitrate.

The addition amount of the water-soluble compound in the raw materialslurry is in the range of 0.01 to 5.0 at a mass ratio to the silicacontained in the colloidal silica (hereinafter, described as “the ratioof the water-soluble compound to the colloidal silica”). The additionamount of the water-soluble compound is in the range of more preferablyfrom 0.03 to 3.0, further more preferably from 0.05 to 2.0, especiallypreferably from 0.1 to 1.0 and extremely preferably from 0.25 to 0.5. Ifthe addition amount of the water-soluble compound is 0.01 or less at amass ratio to the silica obtained by using the colloidal silica as a rawmaterial, the ratio of the void area of the particle cross-sectionbecomes large and the mechanical strength of the particle tends todecrease. If the addition amount of the water-soluble compound is 5.0 ormore at a mass ratio to the silica, when the water-soluble compoundadded is decomposed during the calcining of the catalyst describedlater, the decomposed amount is large. Therefore, excessive pores areformed inside the particle and the mechanical strength of the particletends to decrease. In addition, the drying property of droplets isdeteriorated during the spray drying described later and the adherenceof the raw material slurry to the inside of the spray dryer tends toincrease.

The raw material slurry is preferably acidic. The pH of the raw materialslurry is preferably from 0.01 to 3.0, more preferably from 0.1 to 2.0and especially preferably from 0.5 to 1.5. This is for preventing thatthe colloidal silica is unstabilized and gelated when the water-solublecompound and the colloidal silica coexist in the raw material slurry. Aparticle having high mechanical strength may be obtained by preventingthe gelation of the colloidal silica and spray drying it whilemaintaining the sol state.

In order to form a raw material slurry without gelation of the colloidalsilica, the addition and mixing of each raw material component inpreparing the raw material slurry are preferably carried out by thefollowing methods a) and b).

a) A method of preparing an acidic raw material slurry in which the pHof the slurry obtained by adding the colloidal silica to zeolite ispreliminarily adjusted to acidity by adding an acid such as nitric acid,sulfuric acid and hydrochloric acid and followed by adding awater-soluble compound.

b) A method of preparing an acidic raw material slurry in which the pHof the colloidal silica is preliminarily adjusted to acidity by addingan acid such as nitric acid, sulfuric acid and hydrochloric acid andfollowed by adding a water-soluble compound and then adding zeolite.

The solid content concentration of the raw material slurry after addingzeolite, a colloidal silica, a water-soluble compound and the like ispreferably from 5 to 60% by mass and more preferably from 15 to 40% bymass. In order to adjust the solid content concentration, water may bearbitrarily added to the raw material slurry. Here, the solid contentconcentration of the raw material slurry is a ratio of the mass of theresidue obtained by drying the raw material slurry at 100° C. to thetotal mass of the raw material slurry. The temperature during thepreparation of the raw material slurry is preferably from 5 to 95° C.,more preferably from 10 to 70° C. and especially preferably from 10 to40° C.

When stirring the raw material slurry, the stirring power and stirringtime are selected such that individual raw material components aresufficiently mixed together. The stirring time is preferably from 0.5 to48 hours and more preferably from 1 to 5 hours.

For the purpose of adjusting the mechanical strength, bulk density,shape, catalytic performance and the like of the catalyst particles, theraw material slurry may contain a clay mineral such as kaolin,diatomaceous earth, alumina, titania, zirconia, ceria and the like.These may be added to the raw material slurry in a powder, solution orsol state. In addition, for the purpose of making the shape of thecatalyst particles near a true sphere, a surfactant for adjusting thesurface tension of the raw material slurry may be added to the rawmaterial slurry.

[Step (ii): Drying Step]

The step (ii) is a step of spray drying the raw material slurry obtainedin the above step (i) to obtain dried powders. It is a preferable methodthat the spray drying is carried out using a spray dryer which isindustrially used. The spraying method of the raw material slurry may becarried out by a rotating disk method, a two-fluid nozzle method and ahigh-pressure nozzle method and the like. Among these, an especiallypreferable spraying method is a rotating disk method. The spray dryingmay be carried out by spraying the raw material slurry together with afluid such as air heated by steam and an electric heater, or an inertgas such as nitrogen and helium.

The fluid temperature at a spray dryer inlet is preferably from 100 to400° C. and more preferably from 150 to 300° C. The fluid temperature ata spray dryer outlet is preferably from 80 to 200° C. and morepreferably from 90 to 150° C.

Regarding the spray drying conditions such as the disk rotation numberin the rotating disk method, the spray gas amount in the nozzle method,the feed amount of the raw material slurry, the feeding amount of theheated fluid, and the ratio of these feeding amounts, they may bearbitrarily adjusted so that the adherence of the raw material slurry tothe inside the spray dryer is small and the catalyst particles in astate after calcining have an average particle diameter in the range of20 to 300 μm.

[Step (iii): Calcination Step]

The step (iii) is a step of obtaining calcined particles by calciningthe dried powders obtained in the above step (ii). The calcination ofthe dried powders may be carried out by using a muffle furnace, arotating furnace, a tunnel furnace, a tubular furnace, a fluidizedcalcination furnace, a kiln furnace and the like. An industriallypreferable method is one in which calcination is carried out using acontinuous feed-type rotary kiln furnace. From the viewpoint ofimproving the strength of the catalyst particles, the calcinationtemperature is preferably from 400 to 1000° C. and more preferably from500 to 800° C. From the viewpoint of the strength of the catalystparticles, the calcination time is preferably from 0.1 to 48 hours, morepreferably from 0.5 to 24 hours and further more preferably from 1 to 10hours. The calcination of the dried powders is preferably carried outunder an atmosphere of air, water vapor, or an inert gas such asnitrogen and helium. In addition, the calcination may be carried outunder increased pressure or under reduced pressure. The calcination maybe carried out repeatedly.

In the calcination step, a part or all of the nitrate salt, acetatesalt, carbonate salt, sulfate salt and chloride, which are added as araw material component, may be removed from the dried powders. Inaddition, the dried powders are calcined to sinter silica, therebyenabling dramatically increasing the mechanical strength of the catalystparticles.

[Step (iv): Ion-Exchange Step]

The step (iv) is an ion-exchange step in which an alkali metal componentin the calcined powders is removed by contacting the calcined powdersobtaining in the above step (iii) preferably with a mineral acid and/ora (metal) cation-containing solution, and a cation on the zeolite isconverted into H⁺ or a desired metal cation.

The ion exchange method in the ion-exchange step may be similar to thatof the conventional zeolite-containing catalyst. As the ion-exchangemethod, for example, it is carried out by contacting a mineral acidaqueous solution such as 0.1 to 3 mol concentration of nitric acid,sulfuric acid and hydrochloric acid and/or a (metal) cation-containingaqueous solution such as an ammonium nitrate aqueous solution with thecalcined powders at 10 to 95° C. for 0.1 to 48 hours. Thereafter, theresulting powders are washed with water and dried, followed by againcalcining at 500 to 600° C., if needed.

The production method of the zeolite-containing catalyst of the presentembodiment preferably also has a step in which the calcined powders orpowders passed through the ion-exchanging step are contacted with a gascontaining steam at 500 to 700° C. and then subjected to steamingtreatment. In the zeolite-containing catalyst obtained by the steamingtreatment, the acid property of zeolite is controlled and thedeterioration caused by the formation of a carbonaceous material(coking) during the reaction is suppressed. In addition, if thezeolite-containing catalyst is used, the yield of the target substancemay be increased.

The zeolite-containing catalyst of the present embodiment may becalcined powders obtained by the above calcination step, or powdersobtained by the above ion-exchange step, or powders obtained by theabove step of steaming treatment.

In addition, there are described (ii) spray drying, (iii) calcinationstep and (iv) ion-exchange step as mentioned above. However, from theviewpoint of reducing the sodium content of the resultingzeolite-containing catalyst, if the silica raw material contains waterglass, the spray-dried powders are preferably ion-exchanged beforecalcination. If the spray-dried powders are ion-exchanged after thecalcination step, it tends to be difficult to remove the sodiumcontained in the calcined product.

The production method of the above zeolite-containing catalyst of thepresent embodiment may be applied not only to the production of acatalyst for a fluidized bed reaction, but to the production of acatalyst for a fixed bed reaction. The catalyst for the fixed bedreaction is generally used in a state where an active component such aszeolite is molded with a binder such as silica into a sphere, a tablet,a cylindrical shape, a ring shape, a honeycomb shape and the like havinga diameter of approximately from 1 mm to a few mm. In this case, if theproduction method of the above zeolite-containing catalyst is appliedafter appropriate modification, there may be produced a catalyst for thefixed bed reaction having high mechanical strength and less alkalicontent. If the catalyst has high mechanical strength, it is alsoimportant for a fixed bed catalyst. That is, when a catalyst is filledin a reactor, and when a catalyst is used in a reactor for a long periodof time, if the catalyst has high mechanical strength, cracking andpowderization due to an external stress or a thermal history may besuppressed.

According to the production of the zeolite-containing catalyst of thepresent embodiment, there may be formed strong catalyst particles for afluidized bed reaction in which the void portion inside the particle isextremely small, and the filling state of zeolite and silica has auniform and dense structure. The reason is unclear, but the presentinventors presume as follows. However, the reason is not limited tothis.

Firstly, in preparing particles having an average particle diameter of20 to 300 μm by spray drying the raw material slurry, which containszeolite and a colloidal silica and contains no specific water-solublecompounds relating to the present embodiment, using a well-known method,there occur breakage of particles, and pore opening and depressions onthe particle surface due to the mechanism having the followingprocesses 1) to 3).

Process 1) A liquid vaporizes from the surface of the droplets sprayedto start the contraction of the droplets and then the droplet surface issolidified and contracted mainly by bonding together of the silicaparticles.

Process 2) Thereafter, the liquid continues to vaporize inside thedroplets, but a gas generated by the solidification of the dropletsurface is confined inside the droplets, thereby increasing the internalpressure of the droplet. As a result, the gas is blown out from theinside and there occur breakage (cracking or chipping) of the particlesobtained from the droplet or pore opening and depressions on theparticle surface.

Process 3) After spray drying, when the temperature is decreased, thesurface of the particles is depressed even if the inside of the particlebecomes negative pressure. In the course of these steps, the resultingparticles become brittle because many void portions are formed insidethe particle.

On the other hand, in case of the production method of thezeolite-containing catalyst of the present embodiment, in the aboveprocess 2), since the water-soluble compound added forms a state whereit is adsorbed on the silica particle surface of the colloidal silicaand enters between particles of the silica particles, the silicaparticles are not densely bonded together. For this reason, the moistureinside the particle obtained from droplets is not confined but mayimmediately move from between the silica particles to the outside of theparticles and neither pressure increase nor negative pressurizationinside the particles occurs. As a result, it is presumed that there isformed a structure in which the pore opening of the particle surface orthe void portion inside the particle is extremely little and zeolite andsilica are densely and uniformly filled.

[Production Method of Propylene]

The production method of propylene of the present embodiment comprises astep of contacting the zeolite-containing catalyst with a hydrocarbonand/or an alcohol in a fluidized bed reactor. From the viewpoint ofproducing propylene at a high yield, the hydrocarbon and/or the alcoholwhich are raw materials preferably have a carbon number in the range of2 to 12. From the same viewpoint, the hydrocarbon preferably contains anolefin other than propylene.

The hydrocarbon and/or alcohol which are reaction raw materials are notrequired to be of high quality and may be of industrial grade.

The reaction raw material used for the production method of propylene ofthe present embodiment contains ethylene in an amount of preferably 20%by mass or more and more preferably 25% by mass or more. In addition,water is preferably fed into a reactor together with the raw materialcontaining ethylene. The feed ratio of water is preferably 1 part bymass or more, more preferably from 5 to 100 parts by mass and furthermore preferably from 10 to 80 parts by mass, based on 100 parts by massof the raw material containing ethylene. In addition, in the productionmethod of propylene of the present embodiment, it is a preferredembodiment that propylene is separated from the reaction product and atleast a part of low-boiling components containing the remaining ethyleneand/or high-boiling components containing butene are recycled by feedingthem into the fluidized bed reactor as a raw material.

As the reaction raw material containing ethylene, there may be used oneobtained by the thermal cracking, steam cracking or oxydativedehydrogenation reaction of ethane, or one obtained by the dehydrationreaction of ethanol. The reaction raw material may contain an olefin anda paraffin. The paraffin includes, for example, methane, ethane,propane, butane, pentane, hexane, heptanes, octane and nonane. Inaddition, the olefin includes, for example, propylene, butene, pentene,hexene, heptene, octene and nonene. The reaction raw material containingethylene may contain, in addition to the above compounds, acycloparaffin such as cyclopentane, methylcyclopentane and cyclohexane;a cycloolefin such as cyclopentene, methylcyclopentene and cyclohexene;a diene such as cyclohexadiene, butadiene, pentadiene andcyclopentadiene; and/or an acetylene such as acetylene and methylacetylene. Further, the reaction raw material containing ethylene maycontain an oxygen-containing compound such as t-butylalcohol, methylt-butyl ether, diethyl ether, methyl ethyl ether, dimethyl ether,ethanol and methanol. In addition, the reaction raw material containingethylene may further contain water, hydrogen, nitrogen, carbon dioxideand carbon monoxide.

When the reaction raw material contains ethanol, ethanol (biomassethanol) obtained from plant resources may be used. Such an ethanolspecifically includes ethanol obtained by the fermentation of sugarcaneor corn or the like and ethanol obtained from wood resources such asscrap wood, thinned wood, rice straw and agricultural crops.

The reaction temperature in the fluidized bed reaction is preferablyfrom 300 to 650° C., more preferably from 400 to 600° C. The reactionpressure is preferably from 0.1 to 30 atm. and more preferably from 0.5to 10 atm.

The feed rate of the reaction raw material at a weight hour spacevelocity (WHSV) on the zeolite-containing catalyst basis is preferablyfrom 0.1 to 20 hr⁻¹ and more preferably from 0.5 to 10 hr⁻¹.

In the production method of propylene of the present embodiment, whenthe reaction raw material containing ethylene is used, the conversionrate of ethylene may be controlled by adjusting the above reactionconditions. For example, the reaction conditions are preferablycontrolled so that the conversion rate of ethylene is in the range of 45to 85% and more preferably from 50 to 80%.

In the production method of propylene of the present embodiment, if thezeolite-containing catalyst is used for the reaction for a long periodas a fluidized bed reaction catalyst, a carbonaceous material (coke) isgenerated on the catalyst and the catalytic activity may be decreased.In this case, a part of the zeolite-containing catalyst is taken outcontinuously or intermittently from the fluidized bed reactor and thecoke adhered to the catalyst may be burned and removed using a gascontaining oxygen. In so doing, the zeolite-containing catalyst isregenerated and the zeolite-containing catalyst after regeneration maybe returned to the fluidized bed reactor. In general, the regenerationof the catalyst is carried out in air which is a gas containing oxygenor in an oxygen-containing gas atmosphere at 400 to 700° C.

The zeolite-containing catalyst of the present embodiment has a low voidcontent and has good fluidity and high mechanical strength (attritionresistance). The production method, which is carried out by spray dryingand calcining a specific raw material, is simple. Since thezeolite-containing catalyst of the present embodiment may be used forthe production of propylene and has high mechanical strength, it isespecially suitable as a catalyst for the fluidized bed reaction.

EXAMPLES

Hereinafter, the present invention will be described in detail byshowing Examples, but the present invention is not limited to thefollowing Examples.

[Measurement Methods of Various Physical Properties]

The measurement methods of various physical properties are as follows.

(1) Average Particle Diameter and Particle Size Distribution ofZeolite-Containing Catalyst

The average particle diameter (cumulative particle diameter) and theparticle size distribution of a zeolite-containing catalyst in a stateafter calcination were measured using a laser diffraction/scatteringtype particle size analyzer (manufactured by Microtrac Inc.; trade name,“MT3000”) according to the attached catalog.

(2) Ratio of Void Area of Zeolite-Containing Catalyst

Firstly, the particles of the zeolite-containing catalyst aftercalcination are embedded with a polyester resin, followed by grinding toscrape away the cross-section of the catalyst particles. Subsequently,the cross-section of the catalyst particles which was scraped away wasobserved by an electron microscope (SEM; manufactured by Hitachi, Ltd.;trade name, “S-800”) equipped with an image processing system (ahigh-definition image analysis filing system, manufactured by AsahiChemical Industry Co., Ltd.; trade name, “IP-1000”). In this case,particles having a diameter in the range of ±10% of the average particlediameter were selected. For the selected particles, the cross-sectionarea of one particle and the area of the void portion in thecross-section of the particle, which were observed by at a magnificationof 800 to 2000 times, were measured by the image analysis device.Thereafter, the ratio of the area of the void portion to thecross-section area of the particles measured was calculated. Then, aseries of operations were carried out for 100 particles and thearithmetic average (arithmetical mean) value was defined as the ratio ofvoid area in the cross-section of particles.

In case of a slightly ellipsoidal particle and a particle having adistorted shape, the arithmetic average of the long diameter (thelongest diameter among the diameters passing through the gravity center)and the short diameter (the shortest diameter among the diameterspassing through the gravity center) was defined as a particle diameter.In addition, in case of the particle which has a shape in which a holeis ruptured and the cross-section is observed in a state (C-charactershape) where a part of the circumference is cut, both ends of portions(opening portion) in which a part of the circumference is cut wereconnected with a straight line so as to occlude the opening portion, andthe particle cross-section area and the area of the void portion weredetermined assuming that the straight line is a part of the outercircumference.

(3) Structure Type of Zeolite

The X-ray diffraction pattern of zeolite was measured using a powderX-ray diffraction apparatus (trade name, “RINT”, manufactured by RigakuCo., Ltd.) and the structure type was identified by referring to thewell-known diffraction pattern of zeolite. The measurement conditionswere set as follows: a Cu cathode, the tube voltage: 40 kv, the tubecurrent: 30 mA, the scanning speed: 1 deg/min.

(4) Ratio SiO₂/Al₂O₃ (Molar Ratio) of Zeolite

A dissolution solution was prepared by completely dissolving zeolite ina sodium hydroxide solution. The amount of silicon and aluminumcontained in the dissolution solution was measured by a conventionalmethod using an ICP (inductive-coupled plasma) emission spectrometer(trade name “JY 138”, manufactured by Rigaku Co., Ltd.), and from theresults, the ratio of SiO₂ to Al₂O₃ (mole ratio) was derived. Themeasurement conditions were set as follows: the high frequency power: 1kw, the plasma gas flow rate: 13 L/min, the sheath gas flow rate: 0.15L/min, the nebulizer flow gas rate: 0.25 L/min, the silicone measurementwavelength: 251.60 nm, the aluminum measurement wavelength: 396.152 nm.

(5) Mechanical Strength of Particles of Zeolite-Containing Catalyst

The attrition loss, which is an indicator of mechanical strength ofparticles of a zeolite-containing catalyst, was measured using a jetfluidic apparatus. As the jet fluidic apparatus, there was used anapparatus, in which an orifice with three holes having a diameter of 0.4mm was disposed at a gas introduction portion and which was equippedwith a powder elevating portion having an inside diameter of 35 mm and alength of 700 mm, a powder separating portion having an inside diameterof 110 mm and a length of 600 mm and a fine powder collecting portion.Into the jet fluidic apparatus was charged 52.5 g of azeolite-containing catalyst containing 2.5 g of moisture at roomtemperature, and then air containing moisture in an amount correspondingto the vapor pressure was circulated from a gas introduction portion ata rate of 5.8 NL/min, followed by measuring the mass of fine particlesof the zeolite-containing catalyst, which were collected in a finepowder collecting portion for 0 to 5 hours and 5 to 20 hours after thestart of measurement. And, the attrition loss was determined accordingto the following expression.

Attrition Resistance(% by mass)=A/(B−C)×100

Here, in the above expression, A represents the mass (g) of the fineparticles of the zeolite-containing catalyst collected for 5 to 20 hoursafter the start of measurement, C represents the mass (g) of the fineparticles of the zeolite-containing catalyst collected for 0 to 5 hoursafter the start of measurement, and B represents the total mass (g) ofthe zeolite-containing catalyst used for the test.

(6) Fluidity of Zeolite-Containing Catalyst

The angle of repose, which is an indicator of the fluidity of thezeolite-containing catalyst, was measured using a cylinder rotating-typeangle-of-repose measuring instrument (manufactured by Tsutsui ScientificInstruments Co., Ltd.). To a 500 cc glass sample container (cylindricalmeasurement bottle) was filled 250 cc of a zeolite-containing catalyst,and then the sample container was placed on the upper portion of aroller of the measuring instrument so that the side surface of thecylindrical measurement bottle is contacted with the roller and thecentral axis of the cylindrical measurement bottle is horizontal.Thereafter, while the roller portion was rotated around the central axisof the cylindrical measurement bottle at a rate of 2.4 rpm, the anglefrom the surface of a powder layer inside the cylindrical measurementbottle to the horizontal surface was measured.

(7) Sodium Content of Zeolite-Containing Catalyst

The content of sodium in a zeolite-containing catalyst after calcinationand ion-exchange was measured as follows. Firstly, the catalyst wasdissolved in royal water at 210° C. using a microwave (produced byMilestone Inc., Type: ETOS PLUS) and a small amount of residue wasfiltered. Thereafter, the sodium amount in the filtrate was measured bya conventional method using an ICP emission spectroscopy. From theresult, the content of sodium in the zeolite-containing catalyst wasderived. The measurement conditions was set as follows; the highfrequency power: 1 kw, the plasma gas flow rate: 13 L/min, the sheathgas flow rate: 0.15 L/min: the nebulizer gas flow rate: 0.25 L/min, thesodium measurement wavelength: 589.592 nm.

(8) Calculation of Ethylene Conversion Rate and Propylene Yield

The ethylene conversion rate and the propylene yield were derived fromthe following expressions.

The Ethylene Conversion Rate=(The ethylene concentration in the feedflow at the reactor inlet−The ethylene concentration in the feed flow atthe reactor outlet)/The ethylene concentration in the feed flow at thereactor inlet×100  (a)

The propylene Yield=The mass of propylene generated by the reaction/Themass of ethylene fed in the reactor×100  (b)

[Method for Obtaining Zeolite]

As for MFI-type ZSM-5 used in Examples 1, 5, 6 and 9 and ComparativeExamples 1, 4 and 5, firstly, there were determined the amount ofaluminum sulfate x-hydrate (produced by Wako Pure Chemical Industries,Ltd., special grade reagent) contained in A solution and the amount ofwater glass (trade name, “No. 3 Sodium Silicate”; produced by FujiKagaku Corp.; SiO₂: 29.0% by mass, Na₂O: 9.5% by mass, the balance:water) contained in B solution, so that the molar ratio SiO₂/Al₂O₃ ofthe zeolite is 280. Thereafter, A solution and B solution of that amountwere mixed using a homogenizer at 5000 rpm for 30 minutes, followed byfurther hydrothermally synthesizing at 160° C. for three days (at astirring rate of 600 rpm). Except for the above, zeolite washydrothermally synthesized in the same manner as in Example 2 ofJapanese Patent Publication No. 61-21985 (Japanese Patent Laid-Open No.50-5335).

The resulting zeolite was sufficiently washed with water and dried at120° C., followed by calcining under an air atmosphere in an electricfurnace at 550° C. for 3 hours. Thereafter, in order to convert thecation type of the calcined zeolite into NH₄ ⁺, the zeolite was ionexchanged using a 1 mol concentration of ammonium chloride aqueoussolution at 25° C. for one hour, followed by further washing with waterand drying at 120° C.

In addition, the ratio SiO₂/Al₂O₃ (molar ratio) of the MFI-type ZSM-5,which was measured by the above method, was 280, and the structure typewas identified by the above method. The identification of the structuretype was made by reference to the description in Japanese PatentPublication No. 46-10064 (the same shall apply hereinafter, unlessotherwise specified).

As for MFI-type ZSM-5 used in Examples 2, 10, 11, 12, 13, 17, 23, 24 and25 and Comparative Examples 2, 6, 7 and 9, firstly, zeolite washydrothermally synthesized in the same manner as in Example 3 ofJapanese Patent Publication No. 2-44771 (Japanese Patent Laid-Open No.59-54620) except that a wet cake of the uniform compound D was preparedso that the molar ratio SiO₂/Al₂O₃ of the zeolite is 27.

The resulting zeolite was sufficiently washed with water and dried at120° C. Thereafter, in order to convert the cation type of zeolite intoH⁺, the zeolite was ion-exchanged using a 1 mol concentration of nitricacid aqueous solution at 25° C. for one hour, followed by furtherwashing with water and drying at 120° C.

In addition, the ratio SiO₂/Al₂O₃ (molar ratio) of the MFI-type ZSM-5,which was measured by the above method, was 27, and the structure typewas identified by the above method.

The zeolite was subjected to pulverization treatment using a jet mill(manufactured by Nippon Pneumatic Mfg. Co., Ltd., Type: LJ) so that theaverage particle diameter is 3 μm because the primary particles areaggregated.

As for MFI-type ZSM-5 used in Examples 4 and 21, zeolite washydrothermally synthesized in the same manner as in Example 3 ofJapanese Patent Publication No. 2-44771 (Japanese Patent Laid-Open No.59-54620) except that a wet cake of the uniform compound D was preparedso that the molar ratio SiO₂/Al₂O₃ of the zeolite is 42.

The resulting zeolite was sufficiently washed with water and dried at120° C. Thereafter, in order to convert the cation type of zeolite intoH⁺, the zeolite was ion-exchanged using a 1 mol concentration of nitricacid aqueous solution at 25° C. for one hour, followed by furtherwashing with water and drying at 120° C.

In addition, the ratio SiO₂/Al₂O₃ (molar ratio) of the MFI-type ZSM-5,which was measured by the above method, was 42, and the structure typewas identified by the above method.

As for MFI-type ZSM-5 used in Examples 7, 8, 14, 15, 16, 18 and 19,firstly, there were determined the amount of aluminum sulfate x-hydrate(produced by Wako Pure Chemical Industries, Ltd., special grade reagent)contained in A solution and the amount of water glass (trade name, “No.3 Sodium Silicate”; produced by Fuji Kagaku Corp.; SiO₂: 29.0% by mass,Na₂O: 9.5% by mass, the balance: water) contained in B solution, so thatthe molar ratio SiO₂/Al₂O₃ of the zeolite is 80. Thereafter, A solutionand B solution of that amount were mixed using a homogenizer at 5000 rpmfor 30 minutes, followed by further hydrothermally synthesizing at 160°C. for three days (at a stirring rate of 600 rpm). Except for the above,zeolite was hydrothermally synthesized in the same manner as in Example2 of Japanese Patent Publication No. 61-21985 (Japanese Patent Laid-OpenNo. 50-5335.)

The resulting zeolite was sufficiently washed with water and dried at120° C., followed by calcining under an air atmosphere in an electricfurnace at 550° C. for 3 hours. Thereafter, in order to convert thecation type of the calcined zeolite into NH₄ ⁺, the zeolite was ionexchanged using a 1 mol concentration of ammonium chloride aqueoussolution at 25° C. for one hour, followed by further washing with waterand drying at 120° C.

In addition, the ratio SiO₂/Al₂O₃ (molar ratio) of the MFI-type ZSM-5,which was measured by the above method, was 80, and the structure typewas identified by the above method.

As for MFI-type ZSM-5 used in Example 3 and Comparative Example 3,“MFI-1000” (trade name) produced by Zeolyst International was used.

In addition, the ratio SiO₂/Al₂O₃ (molar ratio) of the MFI-type ZSM-5,which was measured by the above method, was 1000, and the structure typewas identified by the above method.

As for BEA type Beta (β-type zeolite) used in Example 20, “BEA-25”(trade name) produced by PQ Corp. was used.

In addition, the ratio SiO₂/Al₂O₃ (molar ratio) of the β-type zeolite,which was measured by the above method, was 25, and the structure typewas identified by the above method. The identification of the structuretype was made by reference to the description in the specification ofU.S. Pat. No. 3,308,069.

As for MFI-type ZSM-5 used in Example 22, zeolite was hydrothermallysynthesized according to Example 4 of JP Patent No. 3905948. The ratioSiO₂/Al₂O₃ (molar ratio) of the MFI-type ZSM-5, which was measured bythe above method, was 39, and the structure type was identified by theabove method.

As for an ultrastable Y-type (USY) zeolite used in Comparative Example8, zeolite produced by Tosoh Corporation was used.

Example 1

To 2000 g of a colloidal silica (produced by Nalco Company, the silicaaverage particle diameter: 5 nm, the silica content rate: 15% by mass,the sodium content: 185 ppm) was added 40 g of nitric acid (Wako PureChemical Industries, Ltd., a reagent containing 60% by mass of nitricacid, the same shall apply hereinafter) to adjust the pH to 1.1.Thereafter, to the mixture was added 100 g of ammonium nitrate (WakoPure Chemical Industries, Ltd., special grade reagent, the solubility inwater at 0° C.: 118 g/100 g of water, the same shall apply hereinafter),which is a water-soluble compound. Subsequently, to the resultingmixture was added 300 g of MFI-type ZSM-5, in which the molar ratioSiO₂/Al₂O₃ of the zeolite is 280, to prepare a raw material slurry (apreparation step of a raw material mixture). The resulting raw materialslurry was stirred at 25° C. for 3 hours. The raw material slurryexhibited a sol state and had a viscosity of 5 cP (measured by a B-typeviscometer, manufactured by Tokyo Keiki Inc.) The raw material slurrywas spray-dried with a spray dryer to obtain a dried powder (a dryingstep). The raw material slurry was spray dried using a rotating diskmethod by setting the fluid temperature at the spray dryer inlet at 220°C. and the fluid temperature at the spray dryer outlet at 130° C. Theresulting dried powders were calcined using an electric furnace under anair atmosphere at 700° C. for 5 hours (a calcination step).

The resulting calcined powders were mixed with a 0.1 mol concentrationof nitric acid aqueous solution to adjust the solid contentconcentration to 10% by mass, followed by subjecting to ion-exchangetreatment at 25° C. for one hour (an ion-exchange step). Thereafter, theion-exchanged powders through the ion-exchange step were sufficientlywashed with water and dried at 120° C.

On the zeolite-containing catalyst thus obtained, measurements weremade, which included the average particle diameter, angle of repose,mechanical strength (attrition loss) and ratio of void area in thecatalyst particle cross-section in the shape after the calcination(calcined product) as well as the sodium content in the shape after thecalcination and after the ion-exchange (ion-exchanged powders),according to the above-described methods. In addition, the content rateof zeolite, silica and other components was calculated from the feedratio (the same shall apply hereinafter). The measurements values areshown in Table 1. Further, the electron microscope photograph of thecatalyst particles is shown in FIG. 1, and the electron microscopephotograph of the catalyst particle cross-section is shown in FIG. 2.The calcined particles had a particle size distribution in which 95%particles in the whole particles on a volume basis are in the particlediameter range of 2 to 0.2 times the average particle diameter.

Example 2

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for replacing the zeolite with MFI-type ZSM-5 in whichthe molar ratio SiO₂/Al₂O₃ is 27.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 1. In addition,the electron microscope photograph of the catalyst particles is shown inFIG. 3, and the electron microscope photograph of the catalyst particlecross-section is shown in FIG. 4. Further, the electron microscopephotograph of the catalyst particle surface is shown in FIG. 7. A thincrack was observed on the particle surface but the surface had nounevenness.

Example 3

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for replacing the zeolite with MFI-type ZSM-5 in whichthe molar ratio SiO₂/Al₂O₃ is 1000.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 1. In addition,the electron microscope photograph of the catalyst particles is shown inFIG. 5, and the electron microscope photograph of the catalyst particlecross-section is shown in FIG. 6.

Example 4

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for replacing the zeolite with MFI-type ZSM-5 in whichthe molar ratio SiO₂/Al₂O₃ is 42.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 1.

Example 5

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for replacing the water-soluble compound with ammoniumacetate (produced by Wako Pure Chemical Industries, Ltd., special gradereagent, the solubility in water at 4° C.: 148 g/100 g of water).

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 1.

Example 6

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for replacing the colloidal silica with 795 g of acolloidal silica (produced by Nalco Company, a wide range particledistribution type, the silica average particle diameter: 15 nm, thesilica content rate: 38% by mass, the sodium content: 300 ppm) andreplacing the water-soluble compound with ammonium sulfate (produced byWako Pure Chemical Industries, Ltd., special grade reagent, thesolubility in water at 0° C.: 71 g/100 g of water). In addition,purified water was arbitrarily added to the raw material slurry so thatthe solid content concentration of the raw material slurry immediatelybefore spray drying is 30% by mass.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 1.

Example 7

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for replacing the zeolite with MFI-type ZSM-5 in whichthe molar ratio SiO₂/Al₂O₃ is 80 and replacing the water-solublecompound with 72 g of ammonium chloride (produced by Wako Pure ChemicalIndustries, Ltd., special grade reagent, the solubility in water at 0°C.: 29 g/100 g of water).

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 1.

Example 8

A zeolite-containing catalyst was prepared in the same manner as inExample 7 except for replacing the water-soluble compound with 60 g ofammonium carbonate (produced by Wako Pure Chemical Industries, Ltd.,special grade reagent, the solubility in water at 15° C.: 25 g/100 g ofwater).

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 1.

Example 9

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for replacing the colloidal silica with 1800 g of acolloidal silica (produced by Nalco Company, the silica average particlediameter: 5 nm, the silica content rate: 15% by mass, the sodiumcontent: 185 ppm) and replacing the water-soluble compound with 221 g ofaluminum nitrate 9-hydrate (produced by Wako Pure Chemical Industries,Ltd., special grade reagent, the solubility in water at 25° C.: 77.5g/100 g of water).

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 2.

Example 10

A zeolite-containing catalyst was prepared in the same manner as inExample 2 except for replacing the water-soluble compound with 106 g ofsodium nitrate (produced by Wako Pure Chemical Industries, Ltd., specialgrade reagent, the solubility in water at 0° C.: 73 g/100 g of water).

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 2.

Example 11

A zeolite-containing catalyst was prepared in the same manner as inExample 2 except that, in order to reduce the average particle diameterof the zeolite-containing catalyst, the rotation number of the rotatingdisk in spray drying the raw material slurry in the drying step wasincreased.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 2. Thezeolite-containing catalyst had an average particle diameter of 21 μm.

Example 12

A zeolite-containing catalyst was prepared in the same manner as inExample 2 except that, in order to increase the average particlediameter of the zeolite-containing catalyst, the rotation number of therotating disk in spray drying the raw material slurry in the drying stepwas decreased.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 2. Thezeolite-containing catalyst had an average particle diameter of 87 μm.

Example 13

A zeolite-containing catalyst was prepared in the same manner as inExample 2 except that, in order to increase the average particlediameter of the zeolite-containing catalyst, the rotation number of therotating disk in spray drying the raw material slurry and the feedamount of the raw material slurry in the drying step were decreased.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 2. Thezeolite-containing catalyst had an average particle diameter of 293 μm.

Example 14

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for replacing the zeolite with MFI-type ZSM-5 in whichthe molar ratio SiO₂/Al₂O₃ is 80 and changing the amount ofwater-soluble compound to 10 g of ammonium nitrate.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 2.

Example 15

A zeolite-containing catalyst was prepared in the same manner as inExample 14 except for changing the amount of the water-soluble compoundto 30 g of ammonium nitrate.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 2.

Example 16

A zeolite-containing catalyst was prepared in the same manner as inExample 14 except for changing the amount of the water-soluble compoundto 1440 g of ammonium nitrate.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 2.

Example 17

A zeolite-containing catalyst was prepared in the same manner as inExample 2 except for replacing the colloidal silica with 1235 g of acolloidal silica (produced by Nalco Company, the silica average particlediameter: 12 nm, the silica content rate: 34% by mass, the sodiumcontent: 12 ppm), changing the amount of the water-soluble compound to140 g of ammonium nitrate and changing the amount of MFI-type ZSM-5, inwhich the molar ratio SiO₂/Al₂O₃ of the zeolite is 27, to 180 g.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 3.

Example 18

To 3800 g of a colloidal silica (produced by Nalco Company, the silicaaverage particle diameter: 5 nm, the silica content rate: 15% by mass,the sodium content: 185 ppm) was added 60 g of nitric acid to adjust thepH to 1.5. Thereafter, to the mixture was added 188 g of ammoniumnitrate, which is a water-soluble compound. Subsequently, to theresulting mixture was added 30 g of MFI-type ZSM-5, in which the molarratio SiO₂/Al₂O₃ of the zeolite is 80, to prepare a raw material slurry.Except for the above, a zeolite-containing catalyst was prepared in thesame manner as in Example 1.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 3.

Example 19

A zeolite-containing catalyst was prepared in the same manner as inExample 18 except for replacing the colloidal silica with 1200 g of acolloidal silica (produced by Nalco Company, the silica average particlediameter: 5 nm, the silica content rate: 15% by mass, the sodiumcontent: 185 ppm), changing the addition amount of nitric acid to 24 g,changing the amount of the water-soluble compound to 60 g of ammoniumnitrate and changing the amount of MFI-type ZSM-5, in which the molarratio SiO₂/Al₂O₃ is 80, to 420 g.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 3.

Example 20

In the preparation step of the raw material mixture, to a 2800 g of acolloidal silica (produced by Nalco Company, the silica average particlediameter: 5 nm, the silica content rate: 15% by mass, the sodiumcontent: 185 ppm) was added 56 g of nitric acid to adjust the pH to 0.9.To the mixture was added 140 g of ammonium nitrate as a water-solublecompound. Thereafter, to the resulting mixture was added 180 g of aβ-type zeolite, in which the molar ratio SiO₂/Al₂O₃ of the zeolite is25, to prepare a raw material slurry. Except for the above, azeolite-containing catalyst was prepared in the same manner as inExample 1.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 3.

Example 21

A mixture was prepared by adding 300 g of MFI-type ZSM-5, in which themolar ratio SiO₂/Al₂O₃ of the zeolite is 42, to 2000 g of a colloidalsilica (produced by Nalco Company, the silica average particle diameter:5 nm, the silica content rate: 15% by mass, the sodium content: 185ppm). To the mixture was added 40 g of nitric acid to adjust the pH to1.2. Thereafter, to the resulting mixture was added 100 g of ammoniumnitrate, which is a water-soluble compound, to obtain a raw materialslurry (a preparation step of a raw material mixture). Azeolite-containing catalyst was prepared in the same way as in Example 1in the steps that followed.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 3.

Example 22

According to Example 4 of JP Patent No. 3905948, an MFI-type ZSM-5zeolite (the molar ratio SiO₂/Al₂O₃ is 39) was hydrothermallysynthesized. This zeolite slurry as in a slurry state was washed withwater using a rotary filter until the pH becomes 9. Further, the slurrywas ion-exchanged with a 1 mol concentration of sulfuric acid aqueoussolution at 25° C. for one hour and then washed with water until the pHbecomes 4 to obtain 29% by mass of an H⁺ type MFI-type ZSM-5zeolite-containing slurry. A zeolite-containing catalyst was prepared inthe same manner as in Example 1 except for using 1034 g of this slurry(containing 300 g of zeolite) as a raw material zeolite and changing theamount of ammonium nitrate which is a water-soluble compound to 60 g.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 3.

Example 23

To a 1500 g of a colloidal silica (produced by Nalco Company, the silicaaverage particle diameter: 5 nm, the silica content rate: 15% by mass,the sodium content: 185 ppm) was added 98 g of nitric acid to adjust thepH to 0.3. To the mixture was added 75 g of ammonium nitrate, which is awater-soluble compound. Thereafter, to the resulting mixture was addedan aqueous solution obtained by diluting 300 g of water glass (tradename, “Special No. 3 Sodium Silicate”; produced by Fuji Kagaku Corp.;SiO₂: 25.0% by mass, Na₂O: 9.0% by mass, the balance: water, the sameshall apply hereinafter) with 200 g of purified water. In addition, inthis silica sol, 75% by mass of the silica component is made from thecolloidal silica and 25% by mass of the silica component is made fromwater glass. To the mixture was added 300 g of MFI-type ZSM-5, in whichthe molar ratio SiO₂/Al₂O₃ of the zeolite is 27, to prepare raw materialslurry. The raw material slurry had a pH of 1.1.

The raw material slurry was spray dried in the same manner as inExample 1. The resulting dried powders were washed with water at 60 to85° C. for one hour while stirring with 10 L of purified water. Thisoperation was repeated two times. Subsequently, the solid contentconcentration was adjusted to 10% by mass with a 1 mol concentration ofnitric acid aqueous solution, followed by ion-exchanging at 60 to 85° C.for one hour. This operation was repeated two times. Thereafter, theresulting slurry was sufficiently washed with water and dried at 120° C.

The resulting dried powders were calcined using an electric furnaceunder an air atmosphere at 700° C. for one hour.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the ion-exchange and calcinationwere measured. The measurement values are shown in Table 3.

In addition, for reference, a part of the dried powders was collectedand the sodium content before ion-exchange was measured to be 3.27% bymass.

Example 24

There was prepared MFI-type ZSM-5 in which ammonium phosphate wassupported on MFI-type ZSM-5 (the molar ratio SiO₂/Al₂O₃ is 27) used inExample 2 in the following manner. Firstly, a solution was prepared bydissolving 72.2 g of ammonium phosphate (produced by Wako Pure ChemicalIndustries, Ltd., special grade reagent) in 1 L of purified water. Tothe solution was added 500 g of the zeolite. Water was distilled offfrom the resulting slurry by an evaporator under reduced pressure at 60°C. over approximately one hour, and the remaining solid content wascollected and dried, followed by calcining at 500° C. for one hour. Azeolite-containing catalyst was prepared in the same manner as inExample 2 except for replacing the zeolite with 300 g of MFI-type ZSM-5on which the phosphorous component was supported and changing the amountof ammonium nitrate which is a water-soluble compound to 150 g.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 3.

Example 25

To a 1200 g of a colloidal silica (produced by Nalco Company, the silicaaverage particle diameter: 5 nm, the silica content rate: 15% by mass,the sodium content: 185 ppm) was added 160 g of nitric acid to adjustthe pH to 0.1. To the mixture was added 59 g of ammonium nitrate, whichis a water-soluble compound. Thereafter, to the resulting mixture wasadded an aqueous solution obtained by diluting 480 g of water glass(trade name “Special No. 3 Sodium Silicate”, produced by Fuji KagakuCorp.) with 400 g of purified water. In addition, in this silica sol,60% by mass of the silica component is made from the colloidal silicaand 40% by mass of the silica component is made from water glass. To themixture was added 300 g of MFI-type ZSM-5, in which the molar ratioSiO₂/Al₂O₃ of the zeolite is 27, to prepare a raw material slurry. Theraw material slurry had a pH of 0.5.

A zeolite-containing catalyst was prepared in the same manner as inExample 23 after the step of spray drying the raw material slurry.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination and ion-exchangewere measured. The measurement values are shown in Table 3.

In addition, for reference, a part of the dried powders was collectedand the sodium content before ion-exchange was measured to be 5.11% bymass.

Further, the electron microscope photograph of the catalyst particlesurface is shown in FIG. 8.

Example 26

There was produced 500 kg of a zeolite-containing catalyst in the samemanner as in Example 2. The catalyst was filled in a fluidized bedreactor cold model apparatus made of transparent vinyl chloride (theinside diameter: 60 cm, the height: 5 m) which is equipped with acyclone portion. Thereafter, air was fed by a blower from the lowerportion of the equipment at a rate of 700 m³/hr, and the equipment wascontinuously operated for 1000 hours while fluidizing the catalyst at agas linear velocity of 70 cm/sec (on an empty tower basis), which is ona par with an industrial operational condition of a fluidized bedreaction. The catalyst had an attrition loss of 0.20% by mass and anaverage particle diameter of 58 μm after the operation for 1000 hours,and powderization, cracking or chipping of the catalyst was not almostobserved, thereby enabling to continue the operation stably under theindustrial operational condition of the fluidized bed reaction. Theelectron microscope photograph of the catalyst after the operation for1000 hours is shown in FIG. 9.

[Production of Propylene]

Example 27

The zeolite-containing catalyst obtained in Example 2 was subjected tosteaming treatment under the conditions of 650° C., 24 hours, a vaporpartial pressure of 0.8 atm and a nitrogen gas partial pressure of 0.2atm. To a stainless steel fluidized bed reactor having an insidediameter of 1 inch was filled 22.9 g of the catalyst. Thereafter, thefluidized bed reaction was carried out for 100 hours by feedingethylene, hydrogen, water and nitrogen at a flow rate of 9.9 g/hr, 0.7g/hr, 4.9 g/hr and 5.3 g/hr, respectively, under the conditions of areaction temperature of 550° C., a reaction pressure of 0.14 MPa, a WHSVof 0.43 hr⁻¹ (on a zeolite-containing catalyst basis). During thereaction, powderization of the catalyst was not at all observed. Theanalysis of the reaction product was carried out by a gas chromatography(GC-17A, TCD-FID series connection type, manufactured by ShimadzuCorporation) directly connected to the reactor. The process of theethylene conversion rate at each reaction time is shown in FIG. 18. Thepropylene yield in the ethylene conversion rate of 70% was 24.5% bymass.

Example 28

In order to remove the excessive phosphorous component from thezeolite-containing catalyst obtained in Example 24, the catalyst waswashed with water at 25° C. for one hour. The zeolite-containingcatalyst after water washing was subjected to steaming treatment underthe same conditions as in Example 27. The fluidized bed reaction wascarried out using 22.9 g of the catalyst in the same manner as inExample 27. The process of the ethylene conversion rate at each reactiontime is shown in FIG. 18. The propylene yield in the ethylene conversionrate of 70% was 25.5% by mass.

Example 29

The zeolite-containing catalyst after calcination, which was obtained inthe same manner as in Example 17 except that the ion-exchange was notcarried out, was subjected to steaming treatment under the conditions of560° C., 12 hours, a vapor partial pressure of 0.8 atm and a nitrogengas partial pressure of 0.2 atm. The fluidized bed reaction was carriedout using 22.9 g of the catalyst in the same manner as in Example 17.The process of the ethylene conversion rate at each reaction time isshown in FIG. 18. The propylene yield in the ethylene conversion rate of70% was 23.0% by mass.

Example 30

The zeolite-containing catalyst obtained in Example 25 was subjected tosteaming treatment under the same conditions as in Example 27. Thefluidized bed reaction was carried out using 22.9 g of the catalyst inthe same manner as in Example 27. The process of the ethylene conversionrate at each reaction time is shown in FIG. 18. The propylene yield inthe ethylene conversion rate of 70% was 24.0% by mass.

Example 31

The zeolite-containing catalyst obtained in Example 17 was subjected tosteaming treatment under the same conditions as in Example 27. Thefluidized bed reaction was carried out using 22.9 g of the catalyst inthe same manner as in Example 27. The process of the ethylene conversionrate at each reaction time is shown in FIG. 19. The propylene yield inthe ethylene conversion rate of 70% was 24.2% by mass.

Comparative Example 1

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except that ammonium nitrate was not added to the raw materialslurry.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination andion-exchanging were measured. The measurement values are shown in Table4. In addition, the electron microscope photograph of the catalystparticle is shown in FIG. 10 and the electron microscope photograph ofthe catalyst particle cross-section is shown in FIG. 11.

Comparative Example 2

A zeolite-containing catalyst was prepared in the same manner as inExample 2 except that ammonium nitrate was not added to the raw materialslurry.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination andion-exchanging were measured. The measurement values are shown in Table4. In addition, the electron microscope photograph of the catalystparticle is shown in FIG. 12 and the electron microscope photograph ofthe catalyst particle cross-section is shown in FIG. 13.

Comparative Example 3

A zeolite-containing catalyst was prepared in the same manner as inExample 3 except that ammonium nitrate was not added to the raw materialslurry.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination andion-exchanging were measured. The measurement values are shown in Table4. In addition, the electron microscope photograph of the catalystparticle is shown in FIG. 14 and the electron microscope photograph ofthe catalyst particle cross-section is shown in FIG. 15.

Comparative Example 4

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for changing the addition amount of ammonium nitrate to1.5 g in the preparation step of the raw material slurry.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination andion-exchanging were measured. The measurement values are shown in Table4.

Comparative Example 5

A zeolite-containing catalyst was prepared in the same manner as inExample 1 except for changing the addition amount of ammonium nitrate to1800 g in the preparation step of the raw material slurry.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination andion-exchanging were measured. The measurement values are shown in Table4.

Comparative Example 6

A zeolite-containing catalyst was prepared in the same manner as inExample 2 except that, in order to reduce the average particle diameterof the zeolite-containing catalyst, the rotation number of the rotatingdisk in spray drying the raw material slurry in the drying step wasincreased.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination andion-exchanging were measured. The measurement values are shown in Table4. The zeolite-containing catalyst had an average particle diameter of12 μm.

Comparative Example 7

A zeolite-containing catalyst was prepared in the same manner as inExample 2 except that, in order to increase the average particlediameter of the zeolite-containing catalyst, the rotation number of therotating disk in spray drying the raw material slurry and the feedamount of the raw material slurry in the drying step were decreased.

On the zeolite-containing catalyst thus obtained, the above variousphysical properties in the shape after the calcination andion-exchanging were measured. The measurement values are shown in Table4. The zeolite-containing catalyst had an average particle diameter of386 μm.

Comparative Example 8

A catalyst was prepared according to Example 1 of Japanese PatentLaid-Open No. 10-146529. Firstly, a mixture slurry was prepared bymixing an ultrastable Y-type zeolite (produced by Tosoh Corporation),gibbsite having a particle diameter of 1 to 2 μm (aluminum hydroxide,Alcoa), Georgia kaolin, a LUDOX silica sol (HS-40, produced by DuPont,the SiO₂ content rate: 40% by mass) and purified water in the amountdescribed in Example 1 of the patent. Thereafter, an aqueous solutionwas prepared by mixing sulfuric acid (produced by Wako Pure ChemicalIndustries, Ltd., special grade reagent) and aluminum sulfate 15-hydrate(produced by Wako Pure Chemical Industries, Ltd., special grade reagent,the same shall apply hereinafter) in the amount described in Example 1of the patent. To the solution was added an aqueous solution of sodiumsilicate (produced by PQ Corp., “N” brand, the SiO₂ content rate: 28.8%by mass, the Na₂O content rate: 8.9% by mass) in the amount described inExample 1 of the patent. Further, to the resulting solution was added anaqueous solution of aluminum sulfate 15-hydrate of the amount describedin Example 1 of the patent. Finally, to the resulting solution was addedthe firstly prepared mixture slurry to obtain a raw material slurry.

The raw material slurry was spray dried, and the resulting dried powderswere washed with hot water at 85° C. and ion-exchanged with an aqueoussolution of 12% by mass of ammonium sulfate at 85° C. and then washedwith water, followed by finally calcining at 550° C. for 2 hours.

On the catalyst thus obtained, the above various physical propertieswere measured. The measurement values are shown in Table 4. In addition,the electron microscope photograph of the catalyst particle is shown inFIG. 16 and the electron microscope photograph of the catalyst particlecross-section is shown in FIG. 17.

In addition, for reference, a part of the dried powders was collectedand the sodium content before ion-exchange was measured to be 5.36% bymass.

Comparative Example 9

A zeolite-containing catalyst was prepared in the same manner as inComparative Example 8 except that, in order to compare with the reactionperformance (Example 31) of the zeolite-containing catalyst obtained inExample 17, the zeolite which is an active component was changed toMFI-type ZSM-5 in which the molar ratio SiO₂/Al₂O₃ is 27, which was usedin Example 17.

The zeolite-containing catalyst thus obtained was subjected to steamingtreatment in the same manner as in Example 27. The fluidized bedreaction was carried out using 22.9 g of the catalyst in the same manneras in Example 27. The process of the ethylene conversion rate at eachreaction time is shown in FIG. 19.

In addition, for reference, a part of the dried powders was collectedand the sodium content before ion-exchange was measured to be 5.36% bymass.

As is clear from the results shown in Tables 1 to 3, thezeolite-containing catalyst of the present invention had a densestructure in which the void area of the particle cross-section is smalland was excellent in mechanical strength. The particle had a smoothspherical surface and had an angle of repose as measured by the abovemethod, which is an indicator of fluidity, in the range from 25 to 30°.This means that the particle shows the most preferable fluidity, asdescribed in Page 42 of “Fluidized Bed Handbook” (edited by theAssociation of Powder Process Industry & Engineering, Japan, andpublished by Baifukan on Mar. 25, 1999). These facts show that thezeolite-containing catalyst of the present invention has excellentshape, fluidity and strength as a fluidized bed reaction catalyst.

Further, as is clear from the results shown in FIGS. 18 and 19, when thezeolite-containing catalyst of the present invention is used as acatalyst for the fluidized bed reaction for producing propylene from areaction raw material containing ethylene (Examples 27 to 31), it ispossible to stably produce propylene in good yield.

Especially, when a catalyst containing a phosphorous-modified zeolite isused (Example 28), it exhibited higher activity compared to a catalystcontaining a H⁺ type zeolite (Example 27) even after subjecting to thesame steaming treatment, and deterioration with an elapse of time due tocoking was suppressed.

In addition, a zeolite-containing catalyst prepared using a colloidalsilica as in the case of Example 17 exhibited sufficiently high activityby only calcining without ion-exchanging, because the sodium amount inthe catalyst composition is extremely small (Example 29). This leads tothe simplification of the catalyst production step and is extremelyuseful in industrial practical use.

On the other hand, as is clear from the results shown in Table 4, thezeolite-containing catalysts of Comparative Examples (ComparativeExamples 1 to 9) including well-known ones were inferior in mechanicalstrength because the catalysts had many void portions inside theparticle and were inferior in fluidity because the angle of repose wasextremely large as in the case of Comparative Example 6.

In addition, in the zeolite-containing catalyst prepared using a silicasol containing much water glass, it was difficult to obtain a highlyactive catalyst because sodium was insufficiently removed even byion-exchange (Comparative Example 9).

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Raw Water-soluble compound AmmoniumAmmonium Ammonium Ammonium material nitrate nitrate nitrate nitratecomponents Zeolite MFI-type MFI-type MFI-type MFI-type ZSM-5 ZSM-5 ZSM-5ZSM-5 SiO₂/Al₂O₃ [mol ratio] 280 27 1000 42 Water-soluble [wt ratio]0.33 0.33 0.33 0.33 compound/Colloidal silica Colloidal silica [g] 20002000 2000 2000 Nitric acid [g] 40 40 40 40 Water-soluble compound [g]100 100 100 100 Zeolite [g] 300 300 300 300 Viscosity of raw materialslurry [cP] 5 5 6 5 pH of raw material slurry 1.1 0.9 1.2 1.2 CatalystAverage particle diameter [μm] 53 50 52 54 physical Zeolite content rate[wt %] 50 50 50 50 properties Silica content rate [wt %] 50 50 50 50Other components content rate [wt %] 0 0 0 0 Angle of repose [°] 25 2525 25 Void area ratio of cross-section [%] 3 6 4 5 Attrition loss [wt %]0.1 0.2 0.6 0.5 Na content of calcined product [wt %] 0.06 0.06 0.060.06 Na content in ion-exchanged [ppm] 52 55 60 46 product Ex. 5 Ex. 6Ex. 7 Ex. 8 Raw Water-soluble compound Ammonium Ammonium AmmoniumAmmonium material acetate sulfate chloride carbonate components ZeoliteMFI-type MFI-type MFI-type MFI-type ZSM-5 ZSM-5 ZSM-5 ZSM-5 SiO₂/Al₂O₃[mol ratio] 280 280 80 80 Water-soluble [wt ratio] 0.33 0.33 0.24 0.20compound/Colloidal silica Colloidal silica [g] 2000 795 2000 2000 Nitricacid [g] 40 40 40 40 Water-soluble compound [g] 100 100 72 60 Zeolite[g] 300 300 300 300 Viscosity of raw material slurry [cP] 5 6 5 6 pH ofraw material slurry 1.0 1.7 1.0 1.3 Catalyst Average particle diameter[μm] 52 52 54 53 physical Zeolite content rate [wt %] 50 50 50 50properties Silica content rate [wt %] 50 50 50 50 Other componentscontent rate [wt %] 0 0 0 0 Angle of repose [°] 25 27 26 25 Void arearatio of cross-section [%] 10 10 11 12 Attrition loss [wt %] 1.2 1.4 1.81.0 Na content of calcined product [wt %] 0.06 0.04 0.06 0.06 Na contentin ion-exchanged [ppm] 45 32 50 38 product

TABLE 2 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Raw Water-soluble compound AluminiumSodium Ammonium Ammonium material nitrate 9-hydrate nitrate nitratenitrate components Zeolite MFI-type MFI-type MFI-type MFI-type ZSM-5ZSM-5 ZSM-5 ZSM-5 SiO₂/Al₂O₃ [mol ratio] 280 27 27 27 Water-soluble [wtratio] 0.82 0.35 0.33 0.33 compound/Colloidal silica Colloidal silica[g] 1800 2000 2000 2000 Nitric acid [g] 40 40 40 40 Water-solublecompound [g] 221 106 100 100 Zeolite [g] 300 300 300 300 Viscosity ofraw material slurry [cP] 6 6 5 5 pH of raw material slurry 0.9 0.8 0.90.9 Catalyst Average particle diameter [μm] 53 55 21 87 physical Zeolitecontent rate [wt %] 50 47 50 50 properties Silica content rate [wt %] 4547 50 50 Other components content rate [wt %] 5(Al₂O₃) 6(Na₂O) 0 0 Angleof repose [°] 26 26 29 26 Void area ratio of cross-section [%] 18 16 5 6Attrition loss [wt %] 2.5 2.8 0.3 0.2 Na content of calcined product [wt%] 0.06 4.62 0.06 0.06 Na content in ion-exchanged [ppm] 35 14600 40 54product Ex. 13 Ex. 14 Ex. 15 Ex. 16 Raw Water-soluble compound AmmoniumAmmonium Ammonium Ammonium material nitrate nitrate nitrate nitratecomponents Zeolite MFI-type MFI-type MFI-type MFI-type ZSM-5 ZSM-5 ZSM-5ZSM-5 SiO₂/Al₂O₃ [mol ratio] 27 80 80 80 Water-soluble [wt ratio] 0.330.03 0.1 4.8 compound/Colloidal silica Colloidal silica [g] 2000 20002000 2000 Nitric acid [g] 40 40 40 40 Water-soluble compound [g] 100 1030 1440 Zeolite [g] 300 300 300 300 Viscosity of raw material slurry[cP] 5 6 6 6 pH of raw material slurry 0.9 1.0 1.0 0.9 Catalyst Averageparticle diameter [μm] 293 56 54 55 physical Zeolite content rate [wt %]50 50 50 50 properties Silica content rate [wt %] 50 50 50 50 Othercomponents content rate [wt %] 0 0 0 0 Angle of repose [°] 26 26 25 26Void area ratio of cross-section [%] 12 26 18 15 Attrition loss [wt %]1.3 2.5 1.5 2.8 Na content of calcined product [wt %] 0.06 0.06 0.060.06 Na content in ion-exchanged [ppm] 57 58 65 50 product

TABLE 3 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Raw Water-soluble compoundAmmonium Ammonium Ammonium Ammonium Ammonium material nitrate nitratenitrate nitrate nitrate components Zeolite MFI-type MFI-type MFI-typeBEA-type MFI-type ZSM-5 ZSM-5 ZSM-5 Beta ZSM-5 SiO₂/Al₂O₃ [mol ratio] 2780 80 25 42 Water-soluble [wt ratio] 0.33 0.33 0.33 0.33 0.33compound/Collidal silica Colloidal silica [g] 1235 3800 1200 2800 2000Nitric acid [g] 40 60 24 56 40 Water-soluble compound [g] 140 188 60 140100 Zeolite [g] 180 30 420 180 300 Viscosity of raw material slurry [cP]6 5 8 5 6 pH of raw material slurry 0.9 1.5 0.7 0.9 1.2 Catalyst Averageparticle diameter [μm] 51 54 53 53 52 physical Zeolite content rate [wt%] 30 5 70 30 50 properties Silica content rate [wt %] 70 95 30 70 50Other components content rate [wt %] 0 0 0 0 0 Angle of repose [°] 25 2528 25 25 Void area ratio of cross-section [%] 8 5 25 8 8 Attrition loss[wt %] 0.3 0.2 2.8 0.8 0.6 Na content of calcined product [wt %] 0.0020.12 0.04 0.09 0.06 Na content in ion-exchanged product [ppm] 14 98 1867 50 Ex. 22 Ex. 23 Ex. 24 Ex. 25 Raw Water-soluble compound AmmoniumAmmonium Ammonium Ammonium material nitrate nitrate nitrate nitratecomponents Zeolite MFI-type MFI-type MFI-type MFI-type ZSM-5 ZSM-5 ZSM-5ZSM-5 SiO₂/Al₂O₃ [mol ratio] 39 27 27 27 Water-soluble [wt ratio]   0.20    0.33 0.50    0.33 compound/Collidal silica Colloidal silica[g] 2000    1800 (*1) 2000   1680 (*2) Nitric acid [g] 40 98 40 160 Water-soluble compound [g] 60 75 150 59 Zeolite [g]    300 (*3) 300  300300  Viscosity of raw material slurry [cP]  4  5 5  8 pH of raw materialslurry   1.2   1.1 1.0   0.5 Catalyst Average particle diameter [μm] 5152 52 52 physical Zeolite content rate [wt %] 50 48 50   46.5 propertiesSilica content rate [wt %] 50 48 50   46.5 Other components content rate[wt %]  0 4(Na₂O) 0 7(Na₂O) Angle of repose [°] 28 26 25 30 Void arearatio of cross-section [%]  5 15 5 25 Attrition loss [wt %]   0.2   0.80.3   2.3 Na content of calcined product [wt %]    0.06 — 0.06 — Nacontent in ion-exchanged product [ppm] 52 150  62 260  (*1) Representsthe total of the colloidal silica and the water glass (the silicacomponent of the colloidal silica is 75% by mass and the silicacomponent of the water glass is 25% by mass) (*2) Represents the totalof the colloidal silica and the water glass (the silica component of thecolloidal silica is 60% by mass and the silica component of the waterglass is 40% by mass) (*3) Represents the zeolite amount contained inthe raw material zeolite slurry.

TABLE 4 Com. Ex. 1 Com. Ex. 2 Com. Ex. 3 Com. Ex. 4 Com. Ex. 5 RawWater-soluble compound — — — Ammonium Ammonium material nitrate nitratecomponents Zeolite MFI-type MFI-type MFI-type MFI-type MFI-type ZSM-5ZSM-5 ZSM-5 ZSM-5 ZSM-5 SiO₂/Al₂O₃ [mol ratio] 280 27 1000 280 280Water-soluble [wt ratio] — — — 0.005 6.0 compound/Colloidal silicaColloidal silica [g] 2000 2000 2000 2000 2000 Nitric acid [g] 40 40 4040 40 Water-soluble compound [g] 0 0 0 1.5 1800 Zeolite [g] 300 300 300300 300 Viscosity of raw material slurry [cP] 5 6 5 5 6 pH of rawmaterial slurry 1.1 1.2 1.0 0.9 1.0 Catalyst Average particle diameter[μm] 51 53 53 50 54 physical Zeolite content rate [wt %] 50 50 50 50 50properties Silica content rate [wt %] 50 50 50 50 50 Other componentscontent rate [wt %] 0 0 0 0 0 Angle of repose [°] 27 28 27 27 28 Voidarea ratio of cross-section [%] 35 34 40 36 35 Attrition loss [wt %] 6.75.6 25 6.5 5.3 Na content of calcined product [wt %] 0.06 0.06 0.06 0.060.06 Na content in ion-exchanged product [ppm] 53 32 57 56 60 Com. Ex. 6Com. Ex. 7 Com. Ex. 8 Com. Ex. 9 Raw Water-soluble compound AmmoniumAmmonium Aluminum Aluminum material nitrate nitrate sulfate 15- sulfate15- components hydrate hydrate Zeolite MFI-type MFI-type USY MFI-typeZSM-5 ZSM-5 ZSM-5 SiO₂/Al₂O₃ [mol ratio] 27 27  5 27 Water-soluble [wtratio] 0.33 0.33   3.9   3.9 compound/Colloidal silica Colloidal silica[g] 2000 2000   13220 (*1)   13220 (*1) Nitric acid [g] 40 40   2270(*2)   2270 (*2) Water-soluble compound [g] 100 100 5590  5590  Zeolite[g] 300 300 3400  3400  Viscosity of raw material slurry [cP] 6 6  6  6pH of raw material slurry 0.9 0.9   3.2   3.2 Catalyst Average particlediameter [μm] 12 386 52 53 physical Zeolite content rate [wt %] 50 50 2929 properties Silica content rate [wt %] 50 50 35 35 Other componentscontent rate [wt %] 0 0 36 36 Angle of repose [°] 42 28 32 32 Void arearatio of cross-section [%] 8 39 42 40 Attrition loss [wt %] 0.5 7.2  5.2   4.2 Na content of calcined product [wt %] 0.06 0.06 — — Nacontent in ion-exchanged product [ppm] 45 62 420  400  (*1) Representsthe total of the colloidal silica and the water glass (the silicacomponent of the colloidal silica is 34% by mass and the silicacomponent of the water glass is 66% by mass) (*2) Represents thesulfuric acid amount

The present application is based on Japanese Patent Application No.2008-202806 filed on Aug. 6, 2008, the entire contents of which areincorporated herein by reference.

INDUSTRIAL APPLICABILITY

The zeolite-containing catalyst of the present invention may be suitablyused as a catalyst when propylene is produced from a hydrocarbonreaction raw material containing ethylene or the like by a fluidized bedreaction because the catalyst has preferred physical properties as acatalyst for the fluidized bed reaction.

1-8. (canceled)
 9. A zeolite-containing catalyst which is a particulatecatalyst containing zeolite and silica, wherein the catalyst has anaverage particle diameter of 20 to 300 μm and the ratio of the void areain the cross-section of said particle is 30% or less relative to thecross-section area of the particle.
 10. The zeolite-containing catalystaccording to claim 9, wherein said zeolite is an MFI-type zeolite. 11.The zeolite-containing catalyst according to claim 9, wherein thecontent rate of said zeolite is from 10 to 90% by mass, the content rateof said silica is from 10 to 90% by mass, and the total content rate ofsaid zeolite and said silica is 50% by mass or more.
 12. A method forproducing a zeolite-containing catalyst according to claim 9, the methodcomprising: the steps of obtaining a dried powder by spray drying a rawmaterial mixture containing zeolite and colloidal silica; and calciningsaid dried powder, wherein said raw material mixture contains at leastone water-soluble compound selected from the group consisting of anitrate salt, an acetate salt, a carbonate salt, a sulfate salt and achloride in a mass ratio of 0.01 to 5.0 relative to the silica containedin said colloidal silica.
 13. The method for producing azeolite-containing catalyst according to claim 12, wherein the ratio ofthe mass of said colloidal silica to the total amount of silicacontained in said raw material mixture is 50% by mass or more.
 14. Themethod for producing a zeolite-containing catalyst according to claim12, wherein said raw material mixture is acidic.
 15. The method forproducing a zeolite-containing catalyst according to claim 12, whereinsaid water-soluble compound is at least one selected from the groupconsisting of ammonium nitrate, ammonium acetate, ammonium carbonate,ammonium sulfate and ammonium chloride.
 16. A method for producingpropylene comprising the step of contacting a zeolite-containingcatalyst according to claim 9 with a hydrocarbon and/or an alcohol in afluidized bed reactor.
 17. The zeolite-containing catalyst according toclaim 10, wherein the content rate of said zeolite is from 10 to 90% bymass, the content rate of said silica is from 10 to 90% by mass, and thetotal content rate of said zeolite and said silica is 50% by mass ormore.
 18. A method for producing a zeolite-containing catalyst accordingto claim 10, the method comprising: the steps of obtaining a driedpowder by spray drying a raw material mixture containing zeolite andcolloidal silica; and calcining said dried powder, wherein said rawmaterial mixture contains at least one water-soluble compound selectedfrom the group consisting of a nitrate salt, an acetate salt, acarbonate salt, a sulfate salt and a chloride in a mass ratio of 0.01 to5.0 relative to the silica contained in said colloidal silica.
 19. Themethod for producing a zeolite-containing catalyst according to claim18, wherein the ratio of the mass of said colloidal silica to the totalamount of silica contained in said raw material mixture is 50% by massor more.
 20. The method for producing a zeolite-containing catalystaccording to claim 18, wherein said raw material mixture is acidic. 21.The method for producing a zeolite-containing catalyst according toclaim 18, wherein said water-soluble compound is at least one selectedfrom the group consisting of ammonium nitrate, ammonium acetate,ammonium carbonate, ammonium sulfate and ammonium chloride.
 22. Themethod for producing a zeolite-containing catalyst according to claim14, wherein said water-soluble compound is at least one selected fromthe group consisting of ammonium nitrate, ammonium acetate, ammoniumcarbonate, ammonium sulfate and ammonium chloride.
 23. The method forproducing a zeolite-containing catalyst according to claim 20, whereinsaid water-soluble compound is at least one selected from the groupconsisting of ammonium nitrate, ammonium acetate, ammonium carbonate,ammonium sulfate and ammonium chloride.
 24. A method for producingpropylene comprising the step of contacting a zeolite-containingcatalyst according to claim 10 with a hydrocarbon and/or an alcohol in afluidized bed reactor.